Oxygen scavenging compositions and packaging comprising said compositions

ABSTRACT

The instant invention concerns a composition comprising a base polymer, at least one compound of the formula E-(L-E) x  wherein: 
 
E is  
                 
and L is a linking group; and at least one transition metal in a positive oxidation state. The invention also concerns packages containing walls comprising such compositions, methods of forming such packages, and methods of packaging an oxygen-sensitive item within such a package

RELATED APPLICATIONS

This application claims benefit of U.S. Application No. 60/652,888 filedFeb. 15, 2005, the contents of which are incorporated by referenceherein.

FIELD OF THE INVENTION

The present invention relates to substantially transparent compositionsthat comprise a base polymer, an oxidizable organic component, and atransition metal. The invention also concerns use of such compositionsin the construction of packaging for oxygen sensitive materials.

BACKGROUND OF THE INVENTION

It is known in the art to include an oxygen scavenger in the packagingstructure for the protection of oxygen sensitive materials. Suchscavengers are believed to react with oxygen that is trapped in thepackage or that permeates from outside of the package, thus extending tolife of package contents. These packages include films, bottles,containers, and the like. Food, beverages (such as beer and fruitjuices), cosmetics, medicines, and the like are particularly sensitiveto oxygen exposure and require high barrier properties to oxygen topreserve the freshness of the package contents and avoid changes inflavor, texture and color.

Use of certain polyamides in combination with a transition metal isknown to be useful as the oxygen scavenging material. One particularlyuseful polyamide is MXD6 which contains meta-xylene residues in thepolymer chain. See, for example, U.S. Pat. Nos. 5,639,815; 5,049,624;and 5,021,515.

Other oxygen scavengers include potassium sulfite (U.S. Pat. No.4,536,409), unsaturated hydrocarbons (U.S. Pat. No. 5,211,875), andascorbic acid derivatives (U.S. Pat. No. 5,075,362).

In barrier layers of packaging walls that are made from blends of oxygenscavenging materials with base polymer resins such as PET haze canresult due to such factors as: the immiscibility of the scavengingmaterials with the base polymer resins, and the inability to create bymechanical blending means disperse-phase domains that are so small asnot to interfere with the passage of light therethrough; and the adverseinfluence of the scavenging material on the crystallization behavior ofPET base resin. One approach to minimizing such haze is carefulselection of base resin to improve dispersibility of the scavengermaterial and, thus, reduce, but not substantially eliminate, haze; andto minimize the adverse crystallization effect. This approach mayundesirably narrowly restrict the choice of base polymer resin. Anotherapproach is to use compositions that serve as compatibilizers to reducehaze. These approaches add cost to the layer and the compatibilizer addsan additional material that must be evaluated for its suitability forcontact with food. There is a need in the art for barrier materialswhich provide high oxygen scavenging capability and are substantiallytransparent without use of the aforementioned measures.

SUMMARY OF THE INVENTION

The invention relates to a composition which comprises:

(a) at least one base polymer;

(b) at least one non-polymeric oxidizable organic component present inan amount of about 0.10 to 10 weight present of the composition and thecomponent comprising at least one compound of the formula E-(L-E)_(x)wherein:

E is

-   -   L is a linking group of the formula —(O—R₂₁)₂—O—,        —(NH—R₂₁)₂—NH—, —(NH—C(═O)R₂₂)_(t)—NH,        —NH—R₂₅—NH(C(═O)R₂₆NHR₂₅NH)_(u)—, —O—R₂₃—O—R₂₄—C(═O)₅—O— where L        is attached to a carbon atom of Ar (for example, replaces a H        atom of the Ar) in structure (I) or where R₁₂ or R₁₃ of        structure (II) is L;

x is 0, 1, or 2:

Ar is aryl or heteroaryl;

R₁, R₂, and R₁₁ are each independently, H, C₁-C₁₂ alkyl, C₁-C₆ alkoxy,C₆-C₂₀ aryloxy, hydroxy, C₂-C₆ alkenyl, NR₁₉R₂₀, acetyl, nitro,glyceryl, carbohydrate, —C(═O)H, L, or two R₁ or two R₂ groups can forma group of the formula —O—R₁₈—O;

R₃, R₄, R₁₄, and R₁₅ are each H;

R₅ to R₁₀, R₁₆, and R₁₇ are each, independently, H or C₁-C₃ alkyl,

R₁₂ and R₁₃ are each, independently, H, C₁-C₆ alkyl, C₆-C₂₀ aryl, C₁-C₆alkoxy, or L;

R₁₈ is C₂-C₆ alkyl;

R₁₉ and R₂₀ are each, independently, H, C₁-C₆ alkyl, or C₆-C₂₀ aryl;

R₂₁ and R₂₄ are each, independently, C₁-C₆ alkyl;

R₂₂, R₂₃, R₂₅ and R₂₆ are each, independently. C₁-C₆ alkyl or C₆-C₂₀aryl;

n and p are independently 0 or an integer from 1 to 5;

q is 0 or an integer from 1 to 4;

s and z are, independently 1, 2, or 3;

t and u are, independently 1 or 2; and

(c) at least one transition metal in a positive oxidation state, themetal being present in the composition in an amount of 10 to 400 ppm.

Some compounds have R₁, R₂, and R₁₁ as C₁-C₆ alkyl.

In some embodiments, the composition is of the formula:

In some compounds, n and p are each 0, 1, or 2. In certain compounds, R₁and R₂ are each independently H, C₁-C₄ alkyl, hydroxy, C₁-C₃ alkoxy, orcarbohydrate. Some compositions have R₁ and R₂ are each independently H,methyl, ethyl, hydroxy, methoxy, ethoxy, or glucose.

In some embodiments, R₅ to R₁₀ are H. In certain embodiments, R₁ and R₂are each H.

Some compositions are of the formula:

The invention also relates to compositions having the formula:

In some embodiments, R₁₆ and R₁₇ are H. In certain embodiments, each R₁₁is independently H, C₁-C₄ alkyl, hydroxy, or C₁-C₃ alkoxy, orcarbohydrate. In some compositions, each R₁₁ is independently H, methyl,ethyl, hydroxy, methoxy, or ethoxy.

Some compounds have the formula:

Some preferred embodiments have a concentration of transition metal of30 to 150 ppm. In some embodiments, cobalt is the transition metal. Incertain embodiments, the at least one transition metal comprises cobaltand zinc.

In some preferred embodiments, the base polymer comprises a polyesterpolymer. In certain of these embodiments, the polyester polymer ispolyethylene terephthalate.

Some embodiments have the oxidizable organic component present in anamount of about 1 to about 10 weight percent based on the weight of thecomposition. In other embodiments, the oxidizable organic component ispresent in an amount of about 1 to about 5 weight percent based on theweight of the composition. In still other embodiments, the oxidizableorganic component is present in an amount of about 1 to about 3 weightpercent based on the weight of the composition.

The composition can additionally comprise one or more of colorant,filler, crystallization aid, impact modifier, surface lubricant,denesting agent, stabilizer, ultraviolet light absorbing agent, ordyestuff for example.

In some embodiments, the invention concerns a wall for a package, wherethe wall comprising a composition comprising:

at least one base polymer;

at least one non-polymeric oxidizable organic component that is presentin an amount of about 0.10 to 10 weight present of the composition andthe component comprising at least one compound described herein; and

at least one transition metal in a positive oxidation state that ispresent in the composition in an amount of 10 to 400 ppm. In somecompositions, the wall is a single layer. In some embodiments, the wallis multilayer. In the latter embodiment, a first layer can be disposedradially outward from a second layer that contains the oxidizableorganic component.

In another embodiment, the invention relates to a method for packagingan oxygen sensitive material comprising:

(a) preparing a packing having a wall which comprises a compositioncomprising:

-   -   a base polymer;    -   a non-polymeric oxidizable organic component that is present in        an amount of about 0.10 to 10 weight present of the composition        and the component comprising at least one compound described        herein; and    -   at least one transition metal in a positive oxidation state that        is present in the composition in an amount of 10 to 400 ppm;

(b) introducing the oxygen sensitive material into the package, and

(c) closing the package.

In yet other embodiments, the invention concerns a method for producinga container having a wall with oxygen barrier properties comprising:

(a) providing a polymer mixture comprising at least one base polymercontaining at least one non-polymeric oxidizable organic component thatis present in an amount of about 0.10 to 10 weight present of thecomposition and the component comprising at least one compound describedherein; the mixture having at least one transition metal in a positiveoxidation state, the metal being present in the composition in an amountof 10 to 400 ppm;

(b) forming the product of step (a) into a wall; and

(c) forming a container which comprises the wall.

In further embodiments, the invention concerns a process for making anarticle comprising:

(a) forming a melt by combining the following ingredients in a meltprocessing zone:

-   -   a base polymer,    -   a non-polymeric oxidizable organic component that is present in        an amount of about 0.10 to 10 weight present of the composition        and the component comprising at least one compound described        herein;    -   at least one transition metal in a positive oxidation state that        is present in the composition in an amount of 10 to 400 ppm; and

(b) forming an article from the melt.

In certain embodiments, the article is a preform, a sheet, a film, acup, ajar, or a bottle.

In preferred embodiments of the invention, the compositions describedherein are used in monolayer bottles. These compositions areadvantageous in substantially eliminating haze in such compositionscompared to other commercial oxygen scavengers used in monolayerapplications. In other embodiments the compositions are used in one ormore layers of a multi-layer wall of a package, giving protection of thecontents against oxygen without adding haziness to the wall.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows dispersion of 3% monomer-1 in the PET matrix measured usingstandard SEM technique used for evaluating the dispersion of MXD6 nylonin PET versus a dispersion comprising MXD6 (a nylon that is made byMitsubishi Gas Chem) at 3% nominal loading.

FIGS. 2 and 3 show the % oxygen depletion in the vials over time ofsamples having monomers I and II.

FIG. 4 shows oxygen permeation of bottles containing monomer-I that weremounted 2 days after manufacture and 69 days after manufacture.

FIG. 5 shows oxygen permeation of bottles containing monomer-II thatwere mounted 3 days after manufacture and 47 days after manufacture.

FIG. 6 shows evidence of scavenging for compositions containingmonomer-I.

FIG. 7 shows the decrease in oxygen concentration over time for a 3%Monomer-I blend compared to a typical Monoxbar™ MXD6-Co⁺⁺-PET blendcomposition used by Constar in packaging applications.

FIG. 8 shows oxygen permeation rates for 16 and 20 oz hot-fillcontainers that were mounted on an oxygen permeation measuring device 10days later after being stored empty at standard temperature and pressure(STP) conditions.

FIG. 9 shows oxygen permeation rates for 20 oz bottles were blown frompreforms and stored empty for 25 days at STP conditions prior totesting.

FIG. 10 presents a thermogravimetric analysis (TGA) that shows theeffect of residence time on the Monomer-I decomposition in the extruder.

FIG. 11 shows a TGA analysis where a known weight sample of Monomer-Iwas placed in a sample pan and the sample quickly heated (40° C./minheating rate was used) to 280° C. The sample temperature was maintainedat 280° C. for a period of 300 seconds (to simulate typical residencetime in the extruder) and the resulting TGA scan was recorded.

FIGS. 12 and 13 show the percentage oxygen remaining in the vial afterone day as a function of % diamide content and cobalt content.

FIGS. 14 and 15 illustrate the effect of diamine content and extrudertemperatures on the oxygen remaining in the vial after 7 days.

FIGS. 16 and 17 show the interaction of diamide content, extrudertemperatures, and injection cycle time.

FIG. 18 shows oxygen scavenging performance over time.

FIG. 19 shows the effect of PET type in oxygen scavenging performance.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention concerns compositions that are useful in themanufacture of packaging for oxygen sensitive materials. In someembodiments, the invention concerns a polyester polymer composition,preforms, and blow molded containers with good oxygen scavengingproperties as well as substantially reduced haze compared to currentcommercial PET compositions containing an oxygen scavenger comprised ofMXD6 nylon or of Amosorb, an O₂ scavenger containing polybutadieneoligomers.

It is preferred that the non-polymeric oxidizable organic component ofthe instant invention have a high degree of affinity for polyesters.

In certain preferred embodiments, the invention concerns compositionsthat contain a base polymer, a transition metal in a positive oxygenstate, and at least one non-polymeric oxidizable organic componentpresent in an amount of about 0.10 to 10 weight present of thecomposition and the component comprising at least one compound of theformula E-(L-E)_(x) wherein:

E is

L is a linking group of the formula —(O—R₂₁)_(z)—O—, —(NH—R₂₁)_(z)—NH—,—(NH—C(═O)R₂₂)_(t)—NH, —NH—R₂₅—NH(C(═O)R₂₆NHR₂₅NH)_(u)—,—(O—R₂₃—O—R₂₄—C(═O)₅—O— where L is attached to a carbon atom of Ar instructure (I) or where R₁₂ or R₁₃ of structure (II) is L;

x is 0, 1, or 2;

Ar is aryl or heteroaryl;

R₁, R₂, and R₁₁ are each independently, H, C₁-C₁₂ alkyl, C₁-C₆ alkoxy,C₆-C₂₀ aryloxy, hydroxy, C₂-C₆ alkenyl, NR₁₉R₂₀, acetyl, nitro,glyceryl, carbohydrate, —C(═O)H, L, or two R₁ or two R₂ groups can forma group of the formula —O—R₁₈—O;

R₃, R₄, R₁₄, and R₁₅ are each H;

R₅ to R₁₀ and R₁₆, and R₁₇ are each, independently, H or C₁-C₃ alkyl;

R₁₂ and R₁₃ are each, independently, H, C₁-C₆ alkyl, C₆-C₂₀ aryl, C₁-C₆alkoxy, or L;

R₁₈ is C₂-C₆ alkyl;

R₁₉ and R₂₀ are each, independently, H, C₁-C₆ alkyl, or C₆-C₂₀ aryl;

R₂₁ and R₂₄ are each, independently, C₁-C₆ alkyl;

R₂₂, R₂₃, R₂₅ and R₂₆ are each, independently, C₁-C₆ alkyl or C₆-C₂₀aryl;

n and p are independently 0 or an integer from 1 to 5;

q is 0 or an integer from 1 to 4;

s and z are, independently 1, 2, or 3; and

t and u are, independently 1 or 2.

The term “alkyl” refers to a substituted or unsubstituted aliphatichydrocarbon chain. Alkyl groups have straight and branched chains. Insome embodiments, alkyls have from 1 to 12 carbon atoms or 1 to 6 carbonatoms, unless explicitly specified otherwise. Alkyl groups include, burare not limited to methyl, ethyl, propyl, isopropyl, butyl, 1-butyl andt-butyl. Specifically included within the definition of “alkyl” arethose aliphatic hydrocarbon chains that are optionally substituted.

The term “alkoxy,” as used herein, refers to the group R—O— where R isan alkyl group as defined herein.

The term “aryl” is defined herein as an aromatic carbocyclic moiety ofup to 20 carbon atoms. In some embodiments, aryl groups have 6-20 carbonatoms or 6-14 carbon atoms. Aryls may be a single ring (monocyclic) ormultiple rings (bicyclic, up to three rings) fused together or linkedcovalently. Any suitable ring position of the aryl moiety may becovalently linked to the defined chemical structure. Aryl groupsinclude, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl,dihydronaphthyl, tetrahydronaphthyl, biphenyl, anthryl, phenanthryl,fluorenyl, indanyl, biphenylenyl, acenaphthenyl, and acenaphthylenyl. Insome embodiments, phenyl is a preferred aryl. Aryl groups may also beoptionally substituted with one or more substituents.

The term “aryloxy” refers to the group —O—Ar where Ar is an aryl groupas defined herein.

The term “heteroaryl” refers to an aromatic heterocyclic ring system,which may be a single ring (monocyclic) or multiple rings (bicyclic, upto three rings) fused together or linked covalently and having forexample 5 to 20 ring members. The rings may contain from one to fourhetero atoms selected from nitrogen (N), oxygen (O), or sulfur (S),wherein the nitrogen or sulfur atom(s) are optionally oxidized, or thenitrogen atom(s) are optionally substituted (e.g., by alkyl such asmethyl) or quarternized. Any suitable ring position of the heteroarylmoiety may be covalently linked to the defined chemical structure.Exemplary heteroaryl groups include, but are not limited to, pyrryl,furyl, pyridyl, pyridine-N-oxide, 1,2,4-thiadiazolyl, pyrimidyl,thienyl, isothiazolyl, imidazolyl, tetrazolyl, pyrazinyl, pyrimidyl,quinolyl, isoquinolyl, thiophenyl, benzothienyl, isobenzofuryl,pyrazolyl, indolyl, purinyl, carbazolyl, benzimidazolyl, and isoxazolyl.

Optional substituents for alkyl, alkenyl, aryl, or heteroaryl groups arewell known to those skilled in the art. These substituents includealkyl, alkoxy, —SR₁₉, aryloxy, hydroxy, NR₁₉R₂₀, acetyl, cyano, nitro,glyceryl, and carbohydrate, or two substituents taken together may belinked as an -alkylene-group to form a ring. R₁₉ and R₂₀ are as definedherein.

It is believed that some composition, under certain circumstances, canproduce an amount of benzylaldehyde derivative upon decomposition. Assuch, it is desirable that any substituents on aryl groups be ones thatdo not produce a pronounced flavor or odor. Such compositions are easilydetermined by one skilled in the art and can be taken intoconsiderations when selecting substituents for aryl groups.

A surprising result of the oxygen scavenging reaction of some of theseoxygen scavenger materials comprising benzyl amides is that thedecomposition products resulting from the catalytic oxidation bytransition metal in the positive oxidation state, according to thisinvention, (some decomposition products may also result from meltprocessing of the materials) are benzyl aldehydes, which may betoxicologically innocuous. Benzaldehyde, from the oxidativedecomposition of Monomer I, is a natural flavorant, and is generallyrecognized as safe for use in foods or for packaging in contact withfoods. This innocuousness is highly desirable in food packaging. Otherbenzyl amines may be chosen such that the decomposition products arealdehydes that are believed to be innocuous. These include3-methoxy-4-hydroxybenzaldehyde (also known as vanillaldehye orvanillin), 3-ethoxy-2-hydroxybenzaldehyde,4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde,4-hydroxybenzaldehyde-3-sulfonic acid sodium salt,(1,1′-bihenyl)₄-carboxaldehyde, 2-methoxybenzaldehyde4-nitropheynylhydrazone, 3,4,5-triacetoxybenzaldehyde,2-hydroxy-5-methoxybenzaldehyde, 3-benzoxy-4-methoxybenzaldehyde,2-formylbenzenesulfonic acid sodium salt, 4-dodecyloxyenzaldehyde,benzaldehyde-p-sulfonic acid sodium salt, 3-benzoxybenzaldehyde,3-phenoxybenzaldehyde, 5-nitrovanillin, ethyl vanillinbeta-D-glucopyranoside, 1,4-benzodioxan-6-carboxaldehyde,3,4-didecyloxybenzaldehyde, 4-benzyloxy-3-methoxybenzaldehyde,N-ethyl-N-hydroxyethyl-2-methyl-4-aminobenzaldehyde,2,4-dinitrobenzaldehyde, 4-methoxybenzaldehyde-3-sulfonic acid sodiumsalt, 4-benzyloxybenzaldehyde, 4-(4-nitrobenzyloxy)benzaldehyde,4-octylbenzaldehyde, 2-hexyloxybenzaldehyde,3,4-didodecyloxybenzaldehyde, 3,4-dioctyloxybenzaldehyde,3,5-di-tert-butyl-4-hydroxybenzaldehyde, and3-(4-tert-butylphenoxy)benzaldehyde. While the effectiveness inpackaging applications as oxygen scavengers may be somewhat differentfrom one substituted benzyl amine to another, the advantages in thealdehyde decomposition product having reduced sensory detection limitsmay be a good tradeoff, and this can be determined by reasonableexperimentation and testing with the products to be packaged.

In general, it is believed that larger benzaldehydes and their saltshave less intense flavors. It is also believed that benzaldehydes havingat least one sugar substituent will have less flavor than unsubstitutedanalogs. Examples of suitable sugars include glucose, sucrose, andlactose.

“Carbohydrate” as used herein refers to monosaccharides, disaccharides,and trisaccharides. Suitable carbohydrates include glucose, sucrose, andlactose. A carbohydrate substituent may be bound at any suitableposition.

The term “alkenyl” is defined herein as (C₂-C₂₀) straight chain orbranched-chain bivalent hydrocarbon moiety derived from an alkane oralkene that is mono or polyunsaturated. Such groups include those in theE or Z configurations and all possible combinations of E and Zconfigurations. Some preferred alkylene chains have 2-7 carbon atoms.

The carbon number as used in the definitions recited herein refers tocarbon backbone and carbon branching and does not include any carbonatoms that are contained in the optional substituents.

Compositions of the instant invention comprise a base polymer. In someembodiments, the base polymer is a polyester. In certain embodiments,the polyester polymers of the invention are thermoplastic and, thus, theform of the compositions are not limited and can include a compositionin the melt phase polymerization, as an amorphous pellet, as a solidstated polymer, as a semi-crystalline particle, as a composition ofmatter in a melt processing zone, as a bottle preform, or in the form ofa stretch blow molded bottle or other articles. In certain preferredembodiments, the polyester is polyethylene terephthalate (PET).

Examples of suitable polyester polymers include polyethyleneterephthalate homopolymers and copolymers modified with one or morepolycarboxylic acid modifiers in a cumulative amount of less than about15 mole %, or about 10 mole % or less, or about 8 mole % or less, or oneor more hydroxyl compound modifiers in an amount of less than about 60mol %, or less than about 50 mole %, or less than about 40 mole %, orless than about 15 mole %, or about 10 mole % or less, or about 8 mole %or less (collectively referred to for brevity as “PET”) and polyethylenenaphthalate homopolymers and copolymers modified with a cumulativeamount of with less than about 15 mole %, or about 10 mole % or less, orabout 8 mole % or less, of one or more polycarboxylic acid modifiers ormodified less than about 60 mol %, or less than about 50 mole %, or lessthan about 40 mole %, or less than about 15 mole %, or about 10 mole %or less, or about 8 mole % or less of one or more hydroxyl compoundmodifiers (collectively referred to herein as “PEN”), and blends of PETand PEN. A modifier polycarboxylic acid compound or hydroxyl compound isa compound other than the compound contained in an amount of at leastabout 85 mole %. The preferred polyester polymer is polyalkyleneterephthalate, and most preferred is PET.

The polyester compositions can be prepared by polymerization proceduresknown in the art sufficient to effect esterification andpolycondensation. Polyester melt phase manufacturing processes includedirect condensation of a dicarboxylic acid with the diol, optionally inthe presence of esterification catalysts, in the esterification zone,followed by polycondensation in the prepolymer and finishing zones inthe presence of a polycondensation catalyst; or ester exchange usuallyin the presence of a transcsterification catalyst in the ester exchangezone, followed by prepolymerization and finishing in the presence of apolycondensation catalyst, and each may optionally be solid statedaccording to known methods.

Other base polymers may be used with the instant invention. One exampleis polypropylene.

The transition metal used in the instant compositions is a metal in thepositive oxidation state. It should be noted that it is contemplatedthat one or more such metals may be used. In some embodiments, cobalt isadded in +2 or +3 oxidation state. In some embodiments, it is preferredto use cobalt in the +2 oxidation state. In certain embodiments, copperin the +2 oxidation state is utilized. In some embodiments, rhodium inthe +2 oxidation state is used. In certain embodiments, zinc may also beadded to the composition. Preferred zinc compounds include those in apositive oxidation state.

Suitable counter-ions to the transition metal cations includecarboxylates, such as neodecanoates, octanoates, acetates, lactates,naphthalates, malates, stearates, acetylacetonates, linoleates, oleates,palmitates, 2-ethylhexanoates, or ethylene glycolates; or as theiroxides, borates, carbonates, chlorides, dioxides, hydroxides, nitrates,phosphates, sulfates, or silicates among others.

In some embodiments, levels of at least about 10 ppm, or at least about50 ppm, or at least about 100 ppm of metal can achieve suitable oxygenscavenging levels. The exact amount of transition metal used in anapplication can be determined by trials that are well within the skilllevel of one skilled in the art. In some embodiments involving wallapplications (as opposed to master batch applications where morecatalyst is used), it is preferred to keep the level of metal belowabout 300 ppm and, in other embodiments, preferably below about 250 ppm.In master batch compositions, the level of transition metal may rangefrom about 1000 to about 10,000 ppm. In some preferred embodiments, therange is from about 2000 to about 5000 ppm.

The transition metal or metals may be added neat or in a carrier (suchas a liquid or wax) to an extruder or other device for making thearticle, or the metal may be present in a concentrate or carrier withthe oxidizable organic component, in a concentrate or carrier with abase polymer, or in a concentrate or carrier with a basepolymer/oxidizable organic component blend. Alternatively, at least aportion of the transition metal may be added as a polymerizationcatalyst to the melt phase reaction for making the base polymer (apolyester polymer in some embodiments) and be present as residual metalswhen the polymer is fed to the melting zone (e.g. the extrusion orinjection molding zone) for making the article such as a preform orsheet. It is desirable that the addition of the transition metal doesnot substantially increase the intrinsic viscosity (It.V) of the melt inthe melt processing zone. Thus, transition metal or metals may be addedin two or more stages, such as once during the melt phase for theproduction of the polyester polymer and again once more to the meltingzone for making the article.

The compositions of the instant invention comprise at least onenon-polymeric oxidizable organic component present in an amount of about0.10 to 10 weight present of the composition and the componentcomprising at least one compound of the formula E-(L-E)_(x) wherein:

E is

L is a linking group of the formula —(O—R₂₁)_(z)—O—, —(NH—R₂₁)_(z)—NH—,—(NH—C(═O)R₂₂)_(t)—NH, —NH—R₂₅—NH(C(═O)R₂₆NHR₂₅NH)_(u)—,—(O—R₂₃—O—R₂₄—C(═O)_(s)—O— where L is attached to a carbon atom of Ar instructure (I) or where R₁₂ or R₁₃ of structure (II) is L;

x is 0, 1, or 2;

Ar is aryl or heteroaryl;

R₁, R₂, and R₁₁, are each independently, H, C₁-C₁₂ alkyl, C₁-C₆ alkoxy,C₆-C₂₀ aryloxy, hydroxy, C₂-C₆ alkenyl, NR₁₉R₂₀, acetyl, nitro,glyceryl, carbohydrate, —C(═O)H, L, or two R₁ or two R₂ groups can forma group of the formula —O—R₁₈—O;

R₃, R₄, R₁₄, and R₁₅ are each H:

R₅ to R₁₀ and R₁₆, and R₁₇ are each, independently, H or C₁-C₃ alkyl;

R₁₂ and R₁₃ are each, independently, H, C₁-C₆ alkyl, C₆-C₂₀ aryl, C₁-C₆alkoxy, or L;

R₁₈ is C₂-C₆ alkyl;

R₁₉ and R₂₀ are each, independently, H, C₁-C₆ alkyl, or C₆-C₂₀ aryl;

R₂₁ and R₂₄ are each, independently, C₁-C₆ alkyl;

R₂₂, R₂₃, R₂₅ and R₂₆ are each, independently, C₁-C₆ alkyl or C₆-C₂₀aryl:

n and p are independently 0 or an integer from 1 to 5;

q is 0 or an integer from 1 to 4;

s and z are, independently 1, 2, or 3; and

t and u are, independently 1 or 2.

In some embodiments, the compositions comprise at least one monomer ofthe formula:

At least one of these monomers described herein normally will be used inan amount of about 0.1 to about 10 weight percent in an article based onthe weight of the composition. In some preferred embodiments, themonomer(s) will be present in an amount of about 1 to about 5 weightpercent based on the weight of the composition. In other embodiments,the monomer(s) will be present in an amount of about 1 to about 3 weightpercent based on the weight of the composition.

In master batch solutions the amount of monomer will typically be fromabout 10 to about 90 weight percent based on the weight of thecomposition. In some preferred embodiments, the amount of monomer willbe from about 20 to about 80 weight percent based on the weight of thecomposition.

The compounds described herein, including monomers I and II, can be madeby standard synthetic methods known to those skilled in the art. Forexample, one could derive monomer-I by reacting adipic acid and benzylamine. Monomer-II could be made by reacting m-xylene diamne with aformic acid derivative.

In addition, to the monomers discussed in the preceding paragraph. Thecompositions of the invention can contain one or more additional oxygenscavenging materials. These materials may be polymeric, oligomeric, ormonomeric in nature. One suitable material is MXD6, a polyamide, that isdiscussed in U.S. Pat. No. 5,639,815. Other suitable materials arepolyolefins which can be added as blended material or as a unit withinthe base polymer moiety. See, for example, U.S. Pat. No. 6,083,585.

The composition may also include other components such as pigments,fillers, crystallization aids, impact modifiers, surface lubricants,denesting agents, stabilizers, ultraviolet light absorbing agents, metaldeactivators, nucleating agents such as polyethylene and polypropylene,phosphate stabilizers and dyestuffs. Other additional components arewell known to those skilled in the art and can be added to the existingcomposition so long as they do not negatively impact the performance ofthe compositions. In particular, it is known that certain metal ions areto be avoided since they tend to poison the catalytic effect of thetransition metal catalysts of the here-in described invention.Typically, the total quantity of such components will be less than about10% by weight relative to the whole composition. In some embodiments,the amount of these optional components is less than about 5%, by weightrelative to the total composition.

A common additive used in the manufacture of polyester polymercompositions used to make stretch blow molded bottles is a reheatadditive because the preforms made from the composition must be reheatedprior to entering the mold for stretch blowing into a bottle. Any of theconventional reheat additives can be used, such additives includevarious forms of black particles, e.g. carbon black, activated carbon,black iron oxide, glassy carbon, and silicon carbide; the gray particlessuch as antimony, and other reheat additives such as silicas, red ironoxide, and so forth.

In many applications, not only are the packaging contents sensitive tothe ingress of oxygen, but the contents may also be affected by UVlight. Fruit juices and pharmaceuticals are two examples of suchcontents. Accordingly, in some embodiments, it is desirable toincorporate into the polyester composition any one of the known UVabsorbing compounds in amounts effective to protect the packagedcontents so long as the compounds do not negatively impact performance.

The instant compositions can be made by mixing a base polymer (PET, forexample) with the oxidizable organic component and the transition metalcomposition. Such compositions can be made by any method known to thoseskilled in the art. In certain embodiments, some or part of thetransition metal may exist in the base polymer prior to mixing. Thisresidual metal, for example, can exist from the manufacturing process ofthe base polymer. In some embodiments, the base polymer, the oxidizableorganic component and the transition metal are mixed by tumbling in ahopper. Other optional ingredients can be added during this mixingprocess or added to the mixture after the aforementioned mixing or to anindividual component prior to the aforementioned mixing step.

The instant composition can also be made by adding each ingredientseparately and mixing the ingredients prior melt processing thecomposition to form an article. In some embodiments, the mixing can bejust prior to the melt process zone. In other embodiments, one or moreingredients can be premixed in a separate step prior to bringing all ofthe ingredients together.

The oxidizable organic component can be added in pure form or may betreated with a low molecular weight organic wax like compound to preparea pill or bead like material for ease of dosing during the injectionmolding process.

In some embodiments, the invention concerns use of the compositionsdescribed herein as a component of a wall that is used in a package foroxygen sensitive materials. The necessary scavenging capacity of apackage will generally have to be greater for walls that have a greaterpermeance in the absence of scavenging additives. Accordingly, acommercially useful effect is harder to achieve when inherently higherpermeance materials are used, unless the layer is protected, such aswith a layer of polymer or other material, to reduce the O₂ fluxreaching the scavenging composition. Such constructions may findparticular applicability where the requirement is for rapid headspace-O₂evacuation, or in containers for O₂-sensitive products that also requirewalls with low permeance to water vapor.

The wall may be a rigid one, a flexible sheet, or a clinging film. Itmay be homogenous or a laminate or coated with other polymers. If it islaminated or coated, then the scavenging property may reside in a layerof the wall the permeance of which is relatively high in the absence ofscavenging and which alone would not perform very satisfactorily butwhich performs satisfactorily in combination with one or more otherlayers which have a relatively low permeance but negligible orinsufficient oxygen-scavenging properties. A single such layer could beused on the outside of the package since this is the side from whichoxygen primarily comes when the package is filled and sealed. However,such a layer to either side of the scavenging layer would reduceconsumption of scavenging capacity prior to filling and sealing.

When the instant compositions are used in a wall or as a layer of awall, the permeability of the composition for oxygen is advantageouslynot more than about 3.0, or about 1.7, or about 0.7, or about 0.2, orabout 0.03 cm³ mm/(m² atm day). The permeability of the compositionprovided by the present invention is advantageously not more than aboutthree-quarters of that in the absence of oxygen-scavenging properties.In some embodiments, the permeability is not more than about one half,one-tenth in certain embodiments, one twenty-fifth in other embodiments,and not more than one-hundredth in yet other embodiments of that in theabsence of oxygen-scavenging properties. The permeability in the absenceof oxygen-scavenging properties is advantageously not more than about 17cm³ mm/(m² atm day), or about 10, and or about 6. A particularly goodeffect can be achieved for such permeabilities in the range from about0.5, or about 1.0, to 10, or about 6.0, cm³ mm/(m² atm day).Measurements of oxygen permeation can be made by methods described, forexample, in U.S. Pat. No. 5,639,815, the contents of which areincorporated herein in its entirety.

In another aspect, the instant composition can be used as a master batchfor blending with a polymer or a polymer containing component. In suchcompositions, the concentration of the oxidizable organic component andthe transition metal will be higher to allow for the final blendedproduct to have suitable amounts of these components. The master batchmay also contain an amount of the polymer to which the master batch isto be blended with. In other embodiments, the master batch may contain apolymer that is compatible with the polymer that the master batch is tobe blended with.

In yet another aspect, the compositions of the instant invention can beused for forming a layer of a wall which primarily providesoxygen-scavenging (another layer including polymer providing gas barrierwithout significant scavenging), or as a head-space scavenger(completely enclosed, together with the package contents, by a packagewall). Such techniques are well know to those skilled in the art.

The time period for which the permeability is maintained can be extendedby storing the articles in sealed containers or under an inertatmosphere such as nitrogen prior to use with oxygen sensitivematerials. Such a scheme may prove beneficial where performs or rolls offilm or sheet are to be stored for long periods prior to furtherpackaging-conversion operations.

In another aspect, the invention provides a package, whether rigid,semi-rigid, collapsible, lidded, or flexible or a combination of these,comprising a wall as formed from the compositions described herein. Suchpackages can be formed by methods well known to those skilled in theart.

Among the techniques that may be used to make articles are moldinggenerally, injection molding, stretch blow molding, extrusion,thermoforming, extrusion blow molding, and (specifically for multilayerstructures) co-extrusion and lamination using adhesive tie layers.Orientation, e.g. by stretch blow molding, of the polymer is especiallyattractive with phthalate polyesters because of the known mechanicaladvantages that result.

Specific articles include preforms, containers and films for packagingof food, beverages, cosmetics, pharmaceuticals, and personal careproducts where a high oxygen barrier is needed. Examples of beveragecontainers for which the instant invention are particularly useful arebottles for containing juices, sport drinks, beer or any other beveragewhere oxygen detrimentally affects the flavor, fragrance, performance(prevent vitamin degradation), or color of the drink. The compositionsof the instant invention are also particularly useful as a sheet forthermoforming into rigid packages, and as films for flexible-packagestructures. Rigid packages include food trays and lids. Examples of foodtray applications include dual ovenable food trays, or cold storage foodtrays, both in the base container and in the lidding (whether athermoformed lid or a flexible film), where the freshness of the foodcontents can decay with the ingress of oxygen. The compositions of theinstant invention also find use in the manufacture of cosmeticcontainers and containers for pharmaceuticals or medical devices.

The package walls of the instant invention can be a single layer or amultilayer constructions. In some embodiments using multilayer walls,the outer and inner layers may be structural layers with one or morefurther layers. Any of the layers may contain the oxygen scavengingmaterial of this invention. In some embodiments, the outer and innerlayers comprise and polyolefin or a polyester. In the most-preferredembodiments, a single layer design is preferred. Such a design may haveadvantages in simplicity of manufacture and cost, without sacrifice ofthe transparency of the polyester base polymer.

As used herein, the terms “a”, “an”, “the” and the like refer to boththe singular and plural unless the context clearly indicates otherwise.“A bottle”, for example, refers to a single bottle or more than onebottle.

Also as used herein, the description of one or more method steps doesnot preclude the presence of additional method steps before or after thecombined recited steps. Additional steps may also be intervening stepsto those described. In addition, it is understood that the lettering ofprocess steps or ingredients is a convenient means for identifyingdiscrete activities or ingredients and the recited lettering can bearranged in any sequence.

Where a range of numbers is presented in the application, it isunderstood that the range includes all integers and fractions thereofbetween the stated range limits. A range of numbers expressly includesnumbers less than the stated endpoints and those in-between the statedrange. A range of from 1-3, for example, includes the integers one, two,and three as well as any fractions that reside between these integers.

As used herein, “master batch” refers to a mixture of base polymer,oxidizable organic component, and transition metal that will be diluted,typically with at least additional base polymer, prior to forming anarticle. As such, the concentrations of oxidizable organic component andtransition metal are higher than in the formed article.

As used herein, the term “combining” includes blending or reacting thecomponents that are combined.

EXAMPLES

The instant invention is illustrated by the following examples that arenot intended to limit the scope of the invention. N,N′-bis(phenylmethyl)Hexane diamide (referred to as Monomer-I, CAS Registry No: 25344-24-5)and N,N′-[1,3-phenylenebis(methylene)]bis Acetamide (referred to asMonomer-II, CAS Registry No: 131711-99-4) were prepared by SigmaAldrich.

Example 1

Extruded strips were prepared using a bench-top Killion extruder (withtypical extruder output rate between 8-10 lbs/hour) for evaluatingoxygen scavenging potential using oxy-sense™ for Monomer-I andMonomer-II. The temperature profile across different extruder zones usedwas typical to that used for PET (about 525° F.). Extruded films werecut into thin strips and about 2 g samples for each formulation weresealed into 22 mL glass vials and stored at elevated temperature (70°C.). The % oxygen depletion inside the vials over time was monitoredusing commercially available oxy-sense™ instrument. Differentformulations and their respective code names are given below:

1. PET+3% 6007+100 ppm Co carboxylate powder (Code: T10)

2. PET+3% Monomer-I+100 ppm Co carboxylate powder (Code: M-I 3-100)

3. PET+3% Monomer-I+200 ppm Co carboxylate powder (Code: M-I 3-200)

4. PET+5% Monomer-I+100 ppm Co carboxylate powder (Code: M-I 5-100)

5. PET+5% Monomer-I+200 ppm Co carboxylate powder (Code: M-I 5-200)

6. PET+3% Monomer-II+100 ppm Co carboxylate powder (Code: M-II 3-100)

7. PET+3% Monomer-II+200 ppm Co carboxylate powder (Code: M-II 3-200)

8. PET+5% Monomer-II+100 ppm Co carboxylate powder (Code: M-II 5-100)

9. PET+5% Monomer-II+200 ppm Co carboxylate powder (Code: M-II 5-200)

Actual Monomer I and Monomer II content as well as the cobalt content inthe extruded strips were not verified. Graphs in FIGS. 2 and 3 show the% oxygen depletion in the vials over time. It can be seen that whileMonomer-I shows limited scavenging, some of the Monomer-II compositionsscavenge as well as the Monoxbar™ control sample (T10).

It is evident that Monomer-I and Monomer-II have oxygen scavengingpotential based on oxy-sense™ data and further testing was performed bymanufacturing actual blown containers.

Example 2

Preforms were injection molded on a 2 cavity Husky LX160 PET injectionmolding machine. Preforms were made with the following formulations:

Heat Wave™(Voridian) PET+3% Monomer-I+75 ppm Co carboxylate powder

Heat Wave PET+3% Monomer-II+75 ppm Co carboxylate powder

PET, Monomer-I (in powder form) and Cobalt carboxylate mixture (cobaltneodeconate (Co NDA, CAS # 27253-31-2) and cobalt propionate (CAS#1560-69-6) mixture with a 20.5% Co metal content) were tumble blended ina bucket and fed into the machine hopper. Actual final composition inthe preform was not verified. Bottles were blown on the unit cavityRe-heat and blow lab machine for oxygen transmission rate (OTR) and hazemeasurement.

Monomer-I Trial Results:

20 oz bottles were blown form preforms and stored empty at STPconditions prior to testing. Two sets of the empty bottles were mountedon an oxygen permeation measuring device—similar to MoCon Oxtrananalyzer. The first set (A) were mounted 2 days after manufacture, andthe second set (B) were mounted 69 days after manufacture. Results areshown in FIG. 4 where:

A. 2 days after manufacture (—⋄—)

B. 69 days after manufacture (—□—).

Monomer-I Trial Results (Contd.):

A dispersion of Monomer-I in the PET matrix was measured using standardSEM technique used for evaluating the dispersion of nylon in PET. Acomparison of dispersion for the Monomer-I/PET blend compared to MXD6nylon/PET blend, each at 3% nominal loading, is shown in FIG. 1. Itappears that there is significant compatibilization between PET andmonomer matrix compared to that of the MXD6 blend. Percent haze wasmeasured using the hazemeter and the values for Monomer-I blend bottlecompared to that of a plain PET bottle.

Typical haze levels for a 3% Monoxbar formulation would be >15%. It isobvious that there has been significant improvement in the haze levelusing the Monomer-I as the barrier material. The blend formulation isnot perceptibly different in transparency compared to plain PETcontainer. Composition Haze, % (ASTM D1005) 97% PET, 3% MXD6 Blend >1597% PET, 3% Monomer -I 2.7 blend Control 100% PET 3.6Monomer-II Trial Results:

Preforms were molded using Monomer-II material at 3% let down on theHusky molding machine and 16 oz bottles were blown using RHBL. Two setsof bottles were mounted on an oxygen permeation measuring device—similarto MoCon Oxtran analyzer—after being stored empty at STP conditions. Thefirst set (C) were mounted 3 days after manufacture, and the second set(D) were mounted 47 days after manufacture. Results are shown in FIG. 5.

Example 3

Preforms were made on Husky LX 160 PET, 2 cavity machine using thefollowing formulation: Vitiva™ PET+3% N,N′ Bis(phenylmethyl)hexanediamide (Monomer-I)+75 ppm Co. Vitiva PET and Monomer-I powder weretumble blended in a bucket and fed into the machine hopper. Cobalt-NDAdispersed in a liquid hydrocarbon carrier, was introduced using aColorMatrix brand positive displacement pump. Actual final compositionin the preform was verified by performing Nitrogen and ICP analysisBottles were blown on a unit cavity 16 oz blow mold using a Sidel SBO-1machine. Bottles were blown and were mounted on an oxygen permeationmeasuring device—similar to MoCon Oxtran analyzer—13 days aftermanufacture.

Trial Results:

The graph in FIG. 6 shows the OTR performance.

As can be seen from the graph in FIG. 6, some scavenging is evidenced.In order to determine the scavenging potential, samples from the sidewall of the container were sealed into a 20 mL vial and decrease inoxygen % over time was measured using oxy-sense. The graph in FIG. 7shows the decrease in oxygen concentration over time for a 3% Monomer-Iblend compared to a typical Monoxbar™ MXD6-Co⁺⁺-PET blend compositionused by Constar in packaging applications.

Trial Results:

Monomer-I content was measured by performing a nitrogen analysis (Lecomethod) while the cobalt content was determined using inductivelycoupled plasma emission spectroscopy (ICPES) analysis. The results areas follows:

Diamide content: 2.6-2.7%

Co content: 63-71 ppm

Decrease in oxygen concentration observed using the vial test providesevidence for the scavenging ability/potential of Monomer-I in amonolayer blend construction with PET as the base resin. It alsosuggests possible influences of processing conditions on scavenging.

Example 4

Further tests were performed to evaluate thermal effect in manufacturingpreforms on an Arburg machine (different platform) to look at the effectof processing on scavenging. Differences between Husky and Arburginjection machines used for the trials are summarized below: HuskyArburg Screw Diameter 42 mm 25 mm Injection unit P type RS typeHot-runner Yes No # of shots 12-13 2-3 Cycle time 25-26 s 37-39 sApprox. Residence time 250-300 s 80-120 sTrial Results:

Preforms were manufactured using the 20 oz 38 g preform tooling on asingle cavity, 70 ton Arburg injection machine. Preforms were made bytumblin, PET pellets, Monomer-I powder and Cobalt carboxylate powder.The following formulations were used:

1. PET+3% Monomer-I+75 ppm Co

2. PET+5% Monomer-I+75 ppm Co

Preforms were converted into 16 and 20 oz hot-fill containers and weremounted on an oxygen permeation measuring device—similar to MoCon Oxtrananalyzer-10 days later after being stored empty at STP conditions.Results are shown in the graphs in FIG. 8.

The clarity of the bottles produced are excellent with measured OTRresults being as much as an order of magnitude better than the formerexamples, and the induction period is not evident.

Monomer-I content was measured by performing a nitrogen analysis (Lecomethod) while the cobalt content was determined using ICPES analysis forbottles tested on the oxygen permeation apparatus. The results are asfollows: Monomer % Co (ppm) OTR (mL/day) Day 7 2.89 72 0.0064 2.66 700.0121 4.28 67 0.0011 3.82 56 0.0004

Example 4

Trial Results:

A validation trial was performed by manufacturing preforms with 4%monomer-1 content. As previously done, preforms were manufactured usingthe 20 oz 38 g preform tooling on a single cavity, 70 ton Arburginjection machine. Preforms were made by tumbling PET pellets, monomer-1powder and Cobalt carboxylate powder. The following formulation wasused: PET+4% Monomer-I+75 ppm Co.

20 oz bottles were blown from preforms and stored empty at STPconditions prior to testing. Bottles were blown and were mounted on anoxygen permeation measuring device—similar to MoCon Oxtran analyzer 25days later. Results are shown in FIG. 9.

It is evident from the above examples that processing during injectionmolding (extruder sizing, residence time, screw type, injection set-upetc.) have a strong influence on oxygen scavenging performance. In orderto understand the effect of residence time on the Monomer-Idecomposition in the extruder, a thermogravimetric analysis (TGA) wasperformed. A known sample weight was placed in the pan and the sampleheated at a known rate of 10 Deg C./min. and the weight loss that occurswas recorded. This experiment was performed both in nitrogen and airatmosphere. The resultant scans are shown in FIG. 10.

It is clear that the Monomer-I material would undergo some thermaldecomposition in the extruder conditions typically used for themanufacture of PET preforms. In order to understand this further, aknown weight sample of Monomer-I was placed in the sample pan and thesample quickly heated (40° C./min heating rate was used) to 280° C. Thesample temperature was maintained at 280° C. for a period of 300 seconds(to simulate typical residence time in the extruder) and the resultingTGA scan was recorded. The scan is reproduced in FIG. 11.

Results obtained from thermo gravimetric analyzer shown in the aboveexamples, seem to suggest that the residence time would negativelyinfluence the oxygen scavenging performance due to the Monomer-I partlyundergoing thermal decomposition. This correlates well with thescavenging performance seen with Husky and Arburg injection platforms.

Example 5

A design of experiment (DOE) trial was performed on a productioninjection machine to evaluate the effect of monomer-I content andprocess conditions on bottle performance particularly oxygen scavenging.A 9 run factorial experiment was performed with 4 factors—monomer-1content, cobalt content, extruder temperature and cycle time. Previouswork had shown that the material is sensitive to extruder temperatureand residence time and the DOE was planned to study the effect ofprocessing parameters as well as any interaction effect between thedifferent factors.

Test Plan—Experiment #1

Preforms were made on Husky XL 300 PET machine equipped with a 48 cavity38 g preform mold. The monomer-1 material was pre-blended with CobaltNDA at desired let-downs and was fed using a suitable powder feeder(K-tron feeder). The DOE matrix is shown in the table below. Theresponses measured were oxygen transmission rate (Illiop), % oxygenremaining (oxy-sense), IV, and crystallization characteristics (onset).Factor 2 Factor 1 B: Cobalt Factor 3 Factor 4 A: Diamide content C:Temper- D: Cycle Std Run Block % ppm ature Deg C. time sec 7 1 Block 11.5 150 285 27 6 2 Block 1 3 50 285 27 1 3 Block 1 1.5 50 265 27 8 4Block 1 3 150 285 37 2 5 Block 1 3 50 265 37 3 6 Block 1 1.5 150 265 375 7 Block 1 1.5 50 285 37 9 8 Block 1 2.25 100 275 32 4 9 Block 1 3 150265 27

The results were analyzed using a statistical program (Stat-Ease). FIG.12 shows the % oxygen remaining after Day 1 using oxy-sense (scavengingspeed). Analysis shows that increasing the diamide content results inless oxygen remaining in the vial (more scavenging). Interestingly,increasing the cobalt content results in slight increase in oxygenremaining in the vial (FIG. 13). This might indicate presence of anoptimum cobalt level between 50 and 150 ppm for best scavenging.

FIGS. 14 and 15 below show the effect of diamide content and extrudertemperatures on the amount of oxygen remaining in the vial after 7 days(scavenging capacity). Increasing the diamide content results in higherscavenging capacity. Interestingly, higher extruder temperatures show aslight reduction in % oxygen remaining in the vial. This couldpotentially be due to some of the diamide material being already reactedin the extruder and resulting in less material available for scavengingafter bottle manufacture.

Bottles were also mounted on Illiop to get actual oxygen transmissionrate (mL/pkg/day) measurements and were input into the DOE software foranalysis. There were interaction effects between diamide content,extruder temperatures and injection cycle time. Interaction effect plotsare shown in FIGS. 16 and 17.

It can be seen that both increasing the extruder temperature and cycletime (residence time) result in higher OTR (less effective scavenging).Again this seems to indicate that part of the material is alreadyreacted in the extruder and less is actually available for scavengingafter the bottle manufacture.

In order to understand the oxygen scavenging performance over a longtime, bottles from Run #8 (2.25%) and Run #9 (3.0%) were mounted on theIlliop at regular time intervals and the oxygen scavenging performancemonitored (FIG. 18).

Test Plan: Experiment #2

In order to understand the effect of PET type (PET-1 is PET type 1,PET-2 is PET type 2, and PET-3 is PET type 3) on scavenging, bottleswere made with following formulations:

PET-1+2.5% monomer-1+75 ppm Co @ 270 Deg C. extruder temperature

PET-1+2.5% monomer-1+75 ppm Co @ 290 Deg C. extruder temperature

PET-2+2.5% monomer-1+75 ppm Co @ 280 Deg C. extruder temperature

PET-3+2.5% monomer-1+75 ppm Co @ 280 Deg C. extender temperature

PET-1: High CHDM co-polymer resin with UVI/little re-heat additives

PET-2: IPA modified co-polymer no UVI/re-heat additives

PET-3: CHDM modified co-polymer with high amounts of re-heat additive

Samples were cut from the side-wall of the bottle and sealed in 20 mLvials and the scavenging performance was tested using oxy-sense (FIG.19). It is clear that proper selection of PET is important in achievingthe optimum oxygen scavenging performance. PET-1 seems to be thepreferred PET of choice for optimized performance for a givenformulation.

All patents, patent applications and publications described herein areincorporated by reference in their entirety.

1. A composition comprising: (a) at least one base polymer; (b) at leastone non-polymeric oxidizable organic component present in an amount ofabout 0.10 to 10 weight present of the composition and the componentcomprising at least one compound of the formula E-(L-E)_(x) wherein: Eis

L is a linking group of the formula —(O—R₂₁)_(z)—O—, —(NH—R₂₁)_(z)—NH—,—(NH—C(═O)R₂₂)_(t)—NH, —NH—R₂₅—NH(C(═O)R₂₆NHR₂₅NH)_(u)—,—(O—R₂₃—O—R₂₄—C(═O)₅—O— where L is attached to a carbon atom of Ar instructure (I) or where R₁₂ or R₁₃ of structure (II) is L; x is 0, 1, or2; Ar is aryl or heteroaryl; R₁, R₂, and R₁₁ are each independently, H,C₁-C₁₂ alkyl, C₁-C₆ alkoxy, C₆-C₂₀ aryloxy, hydroxy, C₂-C₆ alkenyl,NR₁₉R₂₀, acetyl, nitro, glyceryl, carbohydrate, —C(═O)H, L, or two R₁ ortwo R₂ groups can form a group of the formula —O—R₁₈—O; R₃, R₄, R₁₄, andR₁₅ are each H; R₅ to R₁₀ and R₁₆, and R₁₇ are each, independently, H orC₁-C₃ alkyl; R₁₂ and R₁₃ are each, independently, H, C₁-C₆ alkyl, C₆-C₂₀aryl, C₁-C₆ alkoxy, or L; R₁₈ is C₂-C₆ alkyl; R₁₉ and R₂₀ are each,independently, H, C₁-C₆ alkyl, or C₆-C₂₀ aryl; R₂, and R₂₄ are each,independently, C₁-C₆ alkyl; R₂₂, R₂₃, R₂₅ and R₂₆ are each,independently, C₁-C₆ alkyl or C₆-C₂₀ aryl; n and p are independently 0or an integer from 1 to 5; q is 0 or an integer from 1 to 4; s and zare, independently 1, 2, or 3; t and u are, independently 1 or 2; and(c) at least one transition metal in a positive oxidation state, themetal being present in the composition in an amount of 10 to 400 ppm. 2.The composition of claim 1 having the formula


3. The composition of claim 2 where n and p are each 0, 1, or 2 and R₁and R₂ are each independently H, C₁-C₄ alkyl, hydroxy, C₁-C₃ alkoxy, orcarbohydrate.
 4. The composition of claim 3 wherein R₁ and R₂ are eachindependently H, methyl, ethyl, hydroxy, methoxy, ethoxy, or glucose. 5.The composition of claim 3 where R₅ to R₁₀ are H.
 6. The composition ofclaim 5 where R₁ and R₂ are each H.
 7. The composition of claim 1 havingthe formula:


8. The composition of claim 1 having the formula:


9. The composition of claim 8 where R₁₆ and R₁₇ are H.
 10. Thecomposition of claim 8 where each R₁₁ is independently H, C₁-C₄ alkyl,hydroxy, or C₁-C₃ alkoxy, or carbohydrate.
 11. The composition of claim10 where each R₁₁ is independently H, methyl, ethyl, hydroxy, methoxy,or ethoxy.
 12. The compound of claim 1 having the formula:


13. The composition of claim 1 wherein the at least one transition metalis cobalt.
 14. The composition of claim 13 wherein the at least onetransition metal further comprises zinc.
 15. The composition of claim 1wherein the base polymer comprises a polyester polymer.
 16. Thecomposition of claim 15 wherein the polyester polymer is polyethyleneterephthalate.
 17. The composition of claim 1 wherein the oxidizableorganic component is present in an amount of about 1 to about 10 weightpercent based on the weight of the composition.
 18. The composition ofclaim 1 wherein the oxidizable organic component is present in an amountof about 1 to about 5 weight percent based on the weight of thecomposition.
 19. The composition of claim 1 wherein the oxidizableorganic component is present in an amount of about 1 to about 3 weightpercent based on the weight of the composition.
 20. The composition ofclaim 1 wherein the concentration of transition metal is 30 to 150 ppm.21. An oxygen scavenging material suitable for use in a barrier wallwhose oxidative decomposition products comprise one or more aldehydesthat are toxicologically innocuous.
 22. The material of claim 21 whereinthe aldehydes comprise at least one of benzaldehyde, vanillin,3-ethoxy-2-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde,4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxybenzaldehyde-3-sulfonicacid sodium salt, (1,1′-bihenyl)-4-carboxaldehyde, 2-methoxybenzaldehyde4-nitropheynylhydrazone, 3,4,5-triacetoxybenzaldehyde,2-hydroxy-5-methoxybenzaldehyde, 3-benzoxy-4-methoxybenzaldehyde,2-formylbenzenesulfonic acid sodium salt, 4-dodecyloxyenzaldehyde,benzaldehyde-p-sulfonic acid sodium salt, 3-benzoxybenzaldehyde,3-phenoxybenzaldehyde, 5-nitrovanillin, ethyl vanillinbeta-D-glucopyranoside, 1,4-benzodioxan-6-carboxaldehyde,3,4-didecyloxybenzaldehyde, 4-benzyloxy-3-methoxybenzaldehyde,N-ethyl-N-hydroxyethyl-2-methyl-4-aminobenzaldehyde,2,4-dinitrobenzaldehyde, 4-methoxybenzaldehyde-3-sulfonic acid sodiumsalt, 4-benzyloxybenzaldehyde, 4-(4-nitrobenzyloxy)benzaldehyde,4-octylbenzaldehyde, 2-hexyloxybenzaldehyde,3,4-didodecyloxybenzaldehyde, 3,4-dioctyloxybenzaldehyde,3,5,-di-tert-butyl-4-hydroxybenzaldehyde, and3-(4-tert-butylphenoxy)benzaldehyde.
 23. The material of claim 21wherein the aldehydes comprise benzaldehyde.
 24. A wall of a packagecomprising at least one layer, the layer comprising a composition, thecomposition comprising: (a) at least one base polymer; (b) at least onenon-polymeric oxidizable organic component present in an amount of about0.10 to 10 weight present of the composition and the componentcomprising at least one compound of the formula E-(L-E)_(x) wherein: Eis

L is a linking group of the formula —(O—R₂₁)_(z)—O—, —(NH—R₂₁)_(z)—NH—,—(NH—C(═O)R₂₂)_(t)—NH, —NH—R₂₅—NH(C(═O)R₂H₂₅NH)_(u)—,—(O—R₂₃—O—R₂₄—C(═O)₅—O— where L is attached to a carbon atom of Ar instructure (I) or where R₁₂ or R₁₃ of structure (II) is L; x is 0, 1, or2; Ar is aryl or heteroaryl; R₁, R₂, and R₁₁ are each independently, H,C₁-C₁₂ alkyl, C₁-C₆ alkoxy, C₆-C₂₀ aryloxy, hydroxy, C₂-C₆ alkenyl,NR₁₉R₂₀, acetyl, nitro, glyceryl, carbohydrate, —C(═O)H, L, or two R₁ ortwo R₂ groups can form a group of the formula —O—R₁₈—O; R₃, R₄, R₁₄, andR₁₅ are each H; R₅ to R₁₀ and R₁₆, and R₁₇ are each, independently, H orC₁-C₃ alkyl; R₁₂ and R₁₃ are each, independently, H, C₁-C₆ alkyl, C₆-C₂₀aryl, C₁-C₆ alkoxy, or L; R₁₈ is C₂-C₆ alkyl; R₁₉ and R₂₀ are each,independently, H, C₁-C₆ alkyl, or C₆-C₂₀ aryl; R₂₁ and R₂₄ are each,independently, C₁-C₆ alkyl; R₂₂, R₂₃, R₂₅ and R₂₆ are each,independently, C₁-C₆ alkyl or C₆-C₂₀ aryl; n and p are independently 0or an integer from 1 to 5; q is 0 or an integer from 1 to 4; s and zare, independently 1, 2, or 3; t and u are, independently 1 or 2; and(c) at least one transition metal in a positive oxidation state, themetal being present in the composition in an amount of 10 to 400 ppm.25. A process for making an article comprising: (a) forming a melt bycombining the following ingredients in a melt processing zone: at leastone base polymer, at least one non-polymeric oxidizable organiccomponent present in an amount of about 0.10 to 10 weight present of thecomposition and the component comprising at least one compound of theformula E-(L-E)_(x) wherein: E is

L is a linking group of the formula —(O—R₂₁)_(z)—O—, —(NH—R₂₁)_(z)—NH—,—(NH—C(═O)R₂₂)_(t)—NH, —NH—R₂₅—NH(C(═O)R₂₆NHR₂₅NH)_(u)—,—O—R₂₃—O—R₂₄—C(═O)_(s)—O— where L is attached to a carbon atom of Ar instructure (I) or where R₁₂ or R₁₃ of structure (II) is L; x is 0, 1, or2; Ar is aryl or heteroaryl; R₁, R₂, and R₁₁ are each independently, H,C₁-C₁₂ alkyl, C₁-C₆ alkoxy, C₆-C₂₀ aryloxy, hydroxy, C₂-C₆ alkenyl,NR₁₉R₂₀, acetyl, nitro, glyceryl, carbohydrate, —C(═O)H, L, or two R₁ ortwo R₂ groups can form a group of the formula —O—R₁₈—O; R₃, R₄, R₁₄, andR₁₅ are each H; R₅ to R₁₀ and R₁₆, and R₁₇ are each, independently, H orC₁-C₃ alkyl; R₁₂ and R₁₃ are each, independently, H, C₁-C₆ alkyl, C₆-C₂₀aryl, C₁-C₆ alkoxy, or L; R₁₈ is C₂-C₆ alkyl; R₁₉ and R₂₀ are each,independently, H, C₁-C₆ alkyl, or C₆-C₂₀ aryl; R₂₁ and R₂₄ are each,independently, C₁-C₆ alkyl; R₂₂, R₂₃, R₂₅ and R₂₆ are each,independently, C₁-C₆ alkyl or C₆-C₂₀ aryl; n and p are independently 0or an integer from 1 to 5; q is 0 or an integer from 1 to 4; s and zare, independently 1, 2, or 3; t and u are, independently 1 or 2; (b)forming an article from the melt.
 26. A method for packaging an oxygensensitive material comprising: (a) preparing a package having a wallcomprising at least one layer, at least one of the layers comprising acomposition, the composition comprising at least one base polymer; atleast one non-polymeric oxidizable organic component present in anamount of about 0.10 to 10 weight present of the composition and thecomponent comprising at least one compound of the formula E-(L-E)_(x)wherein: E is

L is a linking group of the formula —(O—R₂₁)_(z)—O—, —(NH—R₂₁)_(z)—NH—,—(NH—C(═O)R₂₂)_(t)—NH, —NH—R₂₅—NH(C(═O)R₂₆NHR₂₅NH)_(u)—,—O—R₂₃—O—R₂₄—C(═O)_(s)—O— where L is attached to a carbon atom of Ar instructure (I) or where R₁₂ or R₁₃ of structure (II) is L; x is 0, 1, or2; Ar is aryl or heteroaryl; R₁, R₂, and R₁₁ are each independently, H,C₁-C₁₂ alkyl, C₁-C₆ alkoxy, C₆-C₂₀ aryloxy, hydroxy, C₂-C₆ alkenyl,NR₁₉R₂₀, acetyl, nitro, glyceryl, carbohydrate, —C(═O)H, L, or two R₁ ortwo R₂ groups can form a group of the formula —O—R₁₈—O; R₃, R₄, R₁₄, andR₁₅ are each H; R₅ to R₁₀ and R₁₆, and R₁₇ are each, independently, H orC₁-C₃ alkyl; R₁₂ and R₁₃ are each, independently, H, C₁-C₆ alkyl, C₆-C₂₀aryl, C₁-C₆ alkoxy, or L; R₁₈ is C₂-C₆ alkyl; R₁₉ and R₂₀ are each,independently, H, C₁-C₆ alkyl, or C₆-C₂₀ aryl; R₂₁ and R₂₄ are each,independently, C₁-C₆ alkyl; R₂₂, R₂₃, R₂₅ and R₂₆ are each,independently, C₁-C₆ alkyl or C₆-C₂₀ aryl; n and p are independently 0or an integer from 1 to 5; q is 0 or an integer from 1 to 4; s and zare, independently 1, 2, or 3; t and u are, independently 1 or 2; and atleast one transition metal in a positive oxidation state, the metalbeing present in the composition in an amount of 10 to 400 ppm. (b)introducing the oxygen sensitive material into the package; and (c)closing the package.
 27. A method for producing a packaging materialhaving a wall with oxygen barrier properties comprising: (a) providingpolymer mixture comprising at least one base polymer containing at leastone non-polymeric oxidizable organic component present in an amount ofabout 0.10 to 10 weight present of the composition and the componentcomprising at least one compound of the formula E-(L-E)_(x) wherein: Eis

L is a linking group of the formula —(O—R₂₁)_(z)—O—, —(NH—R₂₁)_(z)—NH—,—(NH—C(═O)R₂₂)_(t)—NH, —NH—R₂₅—NH(C(═O)R₂₆NHR₂₅NH)_(u)—,—(O—R₂₃—O—R₂₄—C(═O)₅—O— where L is attached to a carbon atom of Ar instructure (I) or where R₁₂ or R₁₃ of structure (II) is L: x is 0, 1, or2; Ar is aryl or heteroaryl; R₁, R₂, and R₁₁ are each independently, H,C₁-C₁₂ alkyl, C₁-C₆ alkoxy, C₆-C₂₀ aryloxy, hydroxy, C₂-C₆ alkenyl,NR₁₉R₂₀, acetyl, nitro, glyceryl, carbohydrate, —C(═O)H, L, or two R₁ ortwo R₂ groups can form a group of the formula —O—R₁₈—O; R₃, R₄, R₁₄, andR₁₅ are each H; R₅ to R₁₀ and R₁₆, and R₁₇ are each, independently, H orC₁-C₃ alkyl; R₁₂ and R₁₃ are each, independently, H, C₁-C₆ alkyl, C₆-C₂₀aryl, C₁-C₆ alkoxy, or L; R₁₈ is C₂-C₆ alkyl; R₁₉ and R₂₀ are each,independently, H, C₁-C₆ alkyl, or C₆-C₂₀ aryl; R₂₁ and R₂₄ are each,independently, C₁-C₆ alkyl; R₂₂, R₂₃, R₂₅ and R₂₆ are each,independently, C₁-C₆ alkyl or C₆-C₂₀ aryl; n and p are independently 0or an integer from 1 to 5; q is 0 or an integer from 1 to 4; s and zare, independently 1, 2, or 3; t and u are, independently 1 or 2;wherein the polymer mixture comprises at least one transition metal in apositive oxidation state, the metal being present in the composition inan amount of 10 to 400 ppm; (b) forming the polymer mixture of step (a)into a wall; and (c) forming a container which comprises the wall.